EP0198795B1 - Procédé de préparation de 1,4-diaminoanthraquinones - Google Patents

Procédé de préparation de 1,4-diaminoanthraquinones Download PDF

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Publication number
EP0198795B1
EP0198795B1 EP86810142A EP86810142A EP0198795B1 EP 0198795 B1 EP0198795 B1 EP 0198795B1 EP 86810142 A EP86810142 A EP 86810142A EP 86810142 A EP86810142 A EP 86810142A EP 0198795 B1 EP0198795 B1 EP 0198795B1
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Prior art keywords
process according
reaction
nitrobenzene
compound
formula
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EP86810142A
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German (de)
English (en)
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EP0198795A3 (en
EP0198795A2 (fr
Inventor
Rudolf Dr. Blattner
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/48—Anthrimides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings

Definitions

  • the present invention relates to a process for the preparation of 1,4-diaminoanthraquinones by oxidation of the corresponding 2,3-dihydro-1,4-diaminoanthraquinones.
  • 1,4-diaminoanthraquinones are usually prepared by heating the corresponding 2,3-dihydro-1,4-diaminoanthraquinones ("Leuko-1, 4-diaminoanthraquinones") with nitrobenzene in the presence of small amounts of an organic base, e.g. Piperidine, manufactured at 130 to 160 ° C.
  • an organic base e.g. Piperidine, manufactured at 130 to 160 ° C.
  • this reaction only provides the desired 1,4-diaminoanthraquinone in relatively poor yield, since appreciable amounts of 1-amino-4-hydroxyanthraquinone and 1-amino-4-anilinoanthraquinone are formed.
  • the object of the present invention was to find a method in which the problems mentioned do not occur or only to a reduced extent.
  • This object is achieved by the process according to the invention by reacting the reaction at a temperature of 100 to 200 ° C. under reduced pressure, at which part of the nitrobenzene is distilled off, carries out.
  • the 1,4-diaminoanthraquinones are obtained in this way in higher yield, the by-products 1-amino-4-hydroxyanthraquinone and 1-amino-4-anilinoanthraquinone being formed in a smaller amount than in the conventional processes.
  • the 1,4-diaminoanthraquinones obtained are either used as such as dyes or serve as intermediates for the preparation of dyes, for example vat dyes. Thanks to the higher purity of the 1,4-diaminoanthraquinone, the dyes mentioned have improved dyeing properties, for example the soiling of polyester fibers is less.
  • the present invention thus relates to a process for the preparation of 1,4-diaminoanthraquinones of the formula (I) wherein R1, R2, R3 and R4 each independently represent hydrogen, alkyl or aryl, by oxidation of a 2,3-dihydro-1,4-diaminoanthraquinone of the formula (2) wherein R1, R2, R3 and R4 have the meaning given, with nitrobenzene, characterized in that the reaction is carried out at a temperature between 100 and 200 ° C under a pressure which is equal to or lower than the vapor pressure of the nitrobenzene at the temperature used.
  • R1, R2, R3 and R4 independently of one another are hydrogen, alkyl, in particular with 1 to 12 carbon atoms, such as e.g. Methyl, ethyl, n-butyl, iso-butyl and n-dodecyl.
  • alkyl is also intended to include substituted alkyl, such as 2-phenylethyl, 2-hydroxyethyl, 5-cyanpentyl, 2-sulfoethyl or 3-dimethylaminopropyl.
  • R1, R2, R3 and R4 may also be optionally substituted aryl, such as e.g. Phenyl or naphthyl, 4-methylphenyl, 4-phenoxyphenyl, 4-biphenylyl, 2,4,6-trimethylphenyl or 4-acetylaminophenyl.
  • R1, R2, R3 and R belot each independently represent hydrogen, C1-C4-alkyl, phenyl or phenyl substituted by C1-C4-alkyl, phenoxy, C1-C4-alkylcarbonyl or phenyl.
  • the process according to the invention is particularly suitable for the preparation of the compound of the formula (1) in which R1, R2, R3 and R4 each represent hydrogen.
  • a compound of the formula (2) is dissolved or suspended in three to four times the amount by weight of nitrobenzene. Subsequently, catalytic amounts of an organic base, in particular piperidine, collidine or di-n-butylamine, and an inorganic basic compound, in particular sodium or potassium carbonate or bicarbonate, are preferably added.
  • an organic base in particular piperidine, collidine or di-n-butylamine
  • an inorganic basic compound in particular sodium or potassium carbonate or bicarbonate
  • the amounts of organic base and of inorganic basic compound correspond to the amounts which are usually used in the oxidation of compounds of the formula (2) with nitrobenzene.
  • the reaction mixture is then heated to 100 to 200 ° C. It has proven to be advantageous if a pressure of ⁇ 100 mbar is selected at the beginning of the heating and this is gradually increased as the temperature rises. After reaching the reaction temperature, which is preferably between 130 and 160 ° C, the pressure is then regulated so that the reaction mixture boils and part of the nitrobenzene is distilled off. The pressure is therefore equal to or lower than the vapor pressure of the nitrobenzene at the temperature used.
  • nitrobenzene Preferably, 3 to 20 mol, in particular 5 to 15 mol, of nitrobenzene are distilled off per mol of compound of the formula (2) during the reaction.
  • the reaction time depends on the reaction conditions, e.g. the temperature.
  • the reaction is preferably carried out at 145 to 160 ° C., in particular 150 to 155 ° C., for 2 to 5 hours.
  • the 1,4-diaminoanthraquinone obtained can be isolated in a conventional manner, e.g. by removing the nitrobenzene by steam distillation, then filtering and drying the filter residue.
  • the 1,4-diaminoanthraquinones obtained by the process are used as dyes or can serve as starting materials for further reactions, for example for the production of further intermediates of the anthraquinone series, such as, for example, sulfonated or benzoylated 1,4-diaminoanthraquinones, and for the production of anthrimides and vat dyes.
  • a preferred variant of the process according to the invention consists in condensing the 1,4-diaminoanthraquinone obtained without isolating it, then with an aromatic, preferably anthraquinone halogen compound to give the anthrimide, the suspension of 1,4-diaminoanthraquinone and the halogen compound being obtained very much quickly, ie heated to reaction temperature within less than 10 minutes, preferably within less than 1 minute and in particular within a maximum of 10 seconds.
  • the preferred procedure is to add the halogen compound to the suspension of 1,4-diaminoanthraquinone and to add this mixture to nitrobenzene which has been heated to the reaction temperature for the formation of anthrimide.
  • the reaction temperature for anthrimide formation is preferably between 180 and 220 ° C, in particular between 195 and 215 ° C.
  • the starting materials, 1,4-diaminoanthraquinone and aromatic halogen compound can be added via separate feeds to the nitrobenzene, which is at the reaction temperature.
  • the aromatic halogen compound is preferably added to the suspension of 1,4-diaminoanthraquinone obtained and the mixture obtained is then metered into the heated nitrobenzene.
  • the condensation reaction takes place in the presence of a basic agent and a copper catalyst.
  • the copper catalyst and the basic compound can be contained in the part of the nitrobenzene which has been heated to the reaction temperature or they can be metered in together with the starting materials.
  • Preferably 5 to 30% by weight of these components are in the nitrobenzene heated to the reaction temperature and the rest is combined with the Educts are metered in, the basic compound also being able to be added in a correspondingly larger amount during the synthesis of the 1,4-diaminoanthraquinone, so that it is contained in the reaction mass obtained.
  • Aromatic halogen compounds are those in which the halogen is bonded directly to the aromatic nucleus. Acid halides of aromatics or compounds that behave similarly to acid halides, e.g. Cyanuric chloride are not to be understood as aromatic halogen compounds.
  • Halogenated anthraquinone, benzanthrone, anthanthrone, pyranthrone, dibenzanthrone, phthaloylacridone, flavanthrone, dibenzopyrenquinone or isoviolanthrone are particularly suitable among these halogenated, optionally substituted by further substituents customary in vat dyes.
  • halogen compound and the linkable amino compound are generally used in approximately stoichiometric amounts, an excess of e.g. However, 10% of one of the components is also possible.
  • Metallic copper and copper compounds such as e.g. Copper oxide or copper-I-chloride in question. Copper and especially copper-I-chloride are preferred.
  • Suitable basic agents are, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium carbonate and potassium carbonate, and also mixtures of these compounds.
  • the amount of copper catalyst required is generally between 0.1 and 1% by weight, based on the anthrimide formed.
  • the anthraquinone imide compounds are isolated in a customary manner, for example by removing the nitrobenzene by steam distillation, then filtering off the condensation product and drying it.
  • the anthraquinone imide compounds obtained are mostly dye intermediates; after conversion into carbazole or acridine derivatives they give vat dyes, which are used for dyeing and printing textile materials such as e.g. Cotton.
  • the procedure is as described in Example 1, but the solution of 1,4-diaminoanthraquinone obtained after completion of the reaction is used directly without further isolation for the preparation of trianthrimide.
  • the reaction mass which has a volume of approximately 180 ml and contains 54.1 g of 1,4-diaminoanthraquinone, is mixed with 116 g of 1-chloroanthraquinone (99%), 50 g of soda, 1.5 g of copper I. -chloride and 320 ml nitrobenzene.
  • Example 2 The procedure is as described in Example 1, but the mixture is heated to 165 ° C. and the vacuum is regulated to approximately 305 mbar. After a reaction time of 1.5 hours and a distillation time of 1 hour, 59.5 g of a product are obtained, which are 89% 1,4-diaminoanthraquinone, 1.1% 1-amino-4-hydroxyanthraquinone and 1.4% 1- Contains amino-4-anilinoanthraquinone.
  • Example 1 The procedure is as described in Example 1, but the reaction temperature is 140 ° C. and the vacuum is regulated at approx. 130 mbar. After a reaction time of 5 hours and a distillation time of 3 hours, 59.5 g of a violet powder are obtained, the quality of which corresponds to that of the product according to Example 1.
  • Example 2 The procedure is as described in Example 1, but the total amount of 520 ml of nitrobenzene is used at the beginning and 340 ml of nitrobenzene are distilled off at a temperature of 150 to 155 ° C. and a pressure of approx. 230 mbar during the four-hour reaction time. A further addition of nitrobenzene and subsequent distillation are eliminated.
  • the reaction mass obtained in this way can be used directly according to Example 2 for the preparation of further intermediates of the anthraquinone series.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (19)

  1. Procédé pour la préparation de 1,4-diaminoanthraquinones de formule (1)
    Figure imgb0012
     dans laquelle R₁, R₂, R₃ et R₄ représentent chacun, indépendamment les uns des autres, un groupe alkyle ou aryle ou un atome d'hydrogène, par oxydation d'une 2,3-dihydro-1,4-diaminoanthraquinone de formule (2)
    Figure imgb0013
     dans laquelle R₁, R₂, R₃ et R₄ ont les significations données, avec le nitrobenzène, caractérisé en ce que l'on effectue la réaction à une température entre 100 et 200°C et sous une pression qui est égale ou inférieure à la tension de vapeur du nitrobenzène à la température utilisée.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on part d'un composé de formule (2) dans lequel R₁, R₂, R₃ et R₄ représentent chacun, indépendamment les uns des autres, un atome d'hydrogène ou un radical alkyle en C₁-C₄, phényle ou phényle substitué par un groupe alkyle en C₁-C₄, phénoxy, alkyl(C₁-C₄)-carbonyle ou phényle.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on part d'un composé de formule (2) dans lequel
    Figure imgb0014
     sont identiques.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'on part d'un composé de formule (2) dans lequel R₁ et R₃ représentent des atomes d'hydrogène.
  5. Procédé selon la revendication 4, caractérisé en ce que l'on part d'un composé de formule (2) dans lequel R₁, R₂, R₃ et R₄ représentent chacun un atome d'hydrogène.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on opère à une température de 130 à 160°C.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que, pendant la réaction, on élimine par distillation de 3 à 20 moles de nitrobenzène par mole de composé de formule (2).
  8. Procédé selon la revendication 7, caractérisé en ce que l'on élimine par distillation de 5 à 15 moles de nitrobenzène par mole de composé de formule (2).
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que l'on effectue la réaction pendant 2 à 5 heures à 145-160°C, en particulier à 150-155°C.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que l'on effectue la réaction en présence d'une base organique.
  11. Procédé selon la revendication 10, caractérisé en ce que l'on utilise en tant que base organique la pipéridine, la collidine ou la di-n-butylamine.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que l'on effectue la réaction en présence d'un composé basique inorganique.
  13. Procédé selon la revendication 12, caractérisé en ce que l'on utilise en tant que composé basique inorganique le carbonate ou bicarbonate de sodium ou de potassium.
  14. Procédé pour la préparation de composés anthraquinonimidiques, caractérisé en ce que l'on oxyde avec le nitrobenzène une 2,3-dihydro-1,4-diaminoanthraquinone de formule
    Figure imgb0015
     dans laquelle R₁ représente un atome d'hydrogène, et R₂, R₃ et R₄ représentent chacun, indépendamment les uns des autres, un atome d'hydrogène ou un groupe alkyle ou aryle, en effectuant la réaction à une température entre 100 et 200°C, sous une pression qui est égale ou supérieure à la tension de vapeur du nitrobenzène à la température utilisée, et en ce que l'on condense ensuite la 1,4-diaminoanthraquinone obtenue, sans l'isoler, avec un composé halogéné aromatique, pour aboutir à l'anthrimide, en portant très rapidement à la température de la réaction la suspension obtenue de la 1,4-diaminoanthraquinone et le composé halogéné.
  15. Procédé selon la revendication 14, caractérisé en ce que l'on effectue la condensation pour la formation de l'anthrimide à une température de 180 à 220°C, de préférence de 195 à 215°C.
  16. Procédé selon la revendication 14 ou 15, caractérisé en ce que l'on ajoute le composé halogéné aromatique à la suspension obtenue de la 1,4-diaminoanthraquinone, et ensuite on ajoute de façon réglée le mélange obtenu au nitrobenzène qui a été porté à la température de réaction pour la formation de l'anthrimide.
  17. Procédé selon la revendication 16, caractérisé en ce que de 5 à 30 % en poids de la substance basique et du catalyseur à base de cuivre sont présents dans le nitrobenzène chauffé à la température de la réaction, et le reste est introduit de façon réglée avec les produits de départ.
  18. Procédé selon l'une des revendications 14 à 17, caractérisé en ce que l'on utilise en tant que composé halogéné une anthraquinone, benzanthrone, anthanthrone, pyranthrone, dibenzanthrone, phtaloylacridone, flavanthrone, dibenzopyrènequinone ou isoviolanthrone halogénée, éventuellement portant d'autres substituants usuels dans les colorants de cuve.
  19. Procédé selon la revendication 18, caractérisé en ce que l'on utilise l'anthraquinone, la benzanthrone, l'anthanthrone, la pyranthrone ou la dibenzanthrone, chlorée ou bromée.
EP86810142A 1985-04-01 1986-03-25 Procédé de préparation de 1,4-diaminoanthraquinones Expired - Lifetime EP0198795B1 (fr)

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CH139985 1985-04-01
CH1399/85 1985-04-01

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EP0198795A2 EP0198795A2 (fr) 1986-10-22
EP0198795A3 EP0198795A3 (en) 1988-11-09
EP0198795B1 true EP0198795B1 (fr) 1991-06-12

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US (1) US4692278A (fr)
EP (1) EP0198795B1 (fr)
JP (2) JPS61246155A (fr)
DE (1) DE3679702D1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0649833B1 (fr) * 1993-10-21 1996-02-28 BASF Aktiengesellschaft Procédé pour la préparation de composés d'amines d'anthraquinone
FR2786484B1 (fr) * 1998-11-30 2001-01-05 Oreal Aminoanthraquinones cationiques, leur utilisation pour la teinture des fibres keratiniques, compositions tinctoriales les renfermant et procedes de teinture
CN109096120A (zh) * 2018-07-20 2018-12-28 江苏华尔化工有限公司 一种1,4-二氨蒽醌隐色体与氧化体混合物的制备工艺

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB270779A (en) * 1926-01-11 1927-05-11 British Dyestuffs Corp Ltd The manufacture and production of anthraquinone intermediates
US2207045A (en) * 1938-03-28 1940-07-09 Nat Aniline & Chem Co Inc Production of aminoanthraquinone compounds
US3040063A (en) * 1960-09-21 1962-06-19 Du Pont Manufacture of anthrimides and anthraquinonylaminobenzanthrones
JPS5192828A (en) * 1975-02-13 1976-08-14 11 aminoantorakinonno kangenseiseiho
JPS58103345A (ja) * 1981-12-11 1983-06-20 Sumitomo Chem Co Ltd トリアンスリミドの製造方法
DE3325277A1 (de) * 1982-07-15 1984-01-26 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von anthrimiden

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JPS61246155A (ja) 1986-11-01
EP0198795A3 (en) 1988-11-09
JPH0322862B2 (fr) 1991-03-27
JPH03128348A (ja) 1991-05-31
US4692278A (en) 1987-09-08
EP0198795A2 (fr) 1986-10-22
DE3679702D1 (de) 1991-07-18
JPH059419B2 (fr) 1993-02-04

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